Surfactant for electrolyte-containing processing solutions

ABSTRACT

Surfactant compositions and baths for specific textile wetprocessing operations are disclosed. The compositions exhibit surfactant qualities even in the presence of up to ten percent (10%) electrolytes including alkalies in the baths and are not adversely affected by water hardness, oxidative reagents or elevated bath temperatures. The compositions include a blend of phosphate esters of 8-carbon alcohols with soluble sulphate esters of alkoxylated alcohols and alkylphenols.

Uite Sttes atet Komor 1 Dec. 3, 1974 SURFACTANT FOR 2,794,004 5/1957Ratti 252/353 ELEQTROLYTE CONTAHNKNG 3,634,024 1/1972 Yelin et a1. 8/1 11 PROCESSING SOLUTIONS Inventor: Joseph A. Komor, Allentown, Pa.

Assignee: GAF Corporation, New York, NY.

Filed: Aug. 28, 1972 Appl. No: 284,250

Related US. Application Data Division of Scr. No 21,197, March 19, 1970,Patv No. 3,704,262.

References Cited UNITED STATES PATENTS 10/1956 Grifo 252/307 PrimaryExaminer-Stephen J. Lechert, Jr.

Assistant Examiner lrwin Gluck Attorney, Agent, or FirmWalter C. Kehm;Samson B. Leavitt [57] ABSTRACT Surfactant compositions and baths forspecific textile wet-processing operations are disclosed. Thecompositions exhibit surfactant qualities even in the presence of up toten percent 10%) electrolytes including alkalies in the baths and arenot adversely affected by water hardness, oxidative reagents or elevatedbath temperatures. The compositions include a blend of phosphate estersof S-carbon alcohols with soluble sulphate esters of alkoxylatedalcohols and alkylphenols.

5 Claims, N0 Drawings SURFACTANT FOR ELECTROLYTE-CONTAINING PROCESSINGSOLUTIONS This is a division of application Ser. No. 21 ,197, filed Mar.19, 1970, now U.S. Pat. No. 3,704,262.

FIELD OF THE INVENTION This invention relates to surfactant compositionsand, more particularly, to such compositions for use in textilewet-processing operations in the presence of high concentrations ofelectrolytes, including alkalies.

BACKGROUND OF THE INVENTION Many textile treatments are wetprocessingoperations. These include scouring, bleaching, dyeing, fixing, weightingand mercerizing among others. Included in such operations are specificoperations that use solutions containing dissolved electrolytes such assalts and alkalies. Sodium Hydroxide, up to ten percent (10%), butusually at seven percent (7%), concentration is a common electrolyteingredient in such baths.

Surfactants are commonly used to enhance the contact between theprocessing solutions and the fibers of the treated textile fabrics. Suchsurface-active agents are also used to increase the rate of penetrationof the processing solutions into the capillaries between the fibers. Theeconomic advantage of increasing the rate of penetration or contact ofany processing operation is readily apparent.

Generally, surfactants improve the overall efficiency of textilewet-processing operations. However, many surfactants which exhibit rapidwetting in tap-water are rendered completely useless in solutionscontaining electrolytes. In turn, those products that provide at leastadequate performance in electrolyte or caustic solutions fail to givesatisfactory wetting in tap-water. This anomaly has necessitated thedevelopment of myriad surfactants, each tailored to meet the specificrequirements of each processing bath. Since many of those surfactants,which are active in the presence of electrolytes, are suitablyeffective, only over very narrow margins of concentrations of specificelectrolytes, each textile plant is required to stock and use manydifferent compositions of electrolytes.

It has long been desired to perfect a single surfactant composition thatwill provide efficient wetting capabilities over the broad range ofelectrolyte contents and concentrations ranging from tap-watercontaining less than 0.01 percent (0.01%) electrolytes to solutionscontaining up to ten percent 10%) electrolytes and including alkalinesolutions equivalent to up to ten percent (l0%)Sodium Hydroxide. Such asingle surfactant composition must be stable in the common baths as wellas in waters of all hardnesses and under ranges of temperaturesextending from room temperatures through the boiling points of thevarious processing solutions.

SUMMARY OF THE INVENTION 6 broad range of commonly encounteredelectrolyte contents including alkalies as individual components or asblended mixtures of alkalies.

The compositions according to the major aspect of this invention may bedescribed as a blend of surfactants including:

a. 30 to 90 parts by weight of the reaction product of an 8-carbonalkanol with a phosphating agent leading to a complex mixture ofphosphate esters, and;

20 the compositions of this invention are effective in improvingwettability at temperatures ranging from 4C. to the boiling points ofthe commonly used electrolytecontaining processing baths such asbleaching and scouring baths.

Another aspect of this invention includes the textile wet-processingbaths containing the blend of surfactants according to this invention.Such baths should contain, in addition to the bath agents, thesurfactant blend according to this invention in the concentration rangeof 0.01 percent (0.01%) to 1 percent (1%) by weight of such baths. Amongthe baths included in the ambit of this invention are the scouring bathscontaining up to ten percent 10%) by weight of alkali or alkaliequivalents, i.e., sodium sulphate, etc.; and alkaline 5 bleaching bathsincluding peroxides, perborates,

isocyanurates, etc., as oxidizers as well as buffering electrolytes. Theinvention has proven particularly useful in such baths.

Another aspect of this invention includes the process of using bathscontaining these novel compositions for the wetprocessing of textilesand includes the processes of scouring and bleaching with such baths.Similar operations including dyeing, rinsing and washing utilizing theimprovements in such operations resulting from the improved wettabilityderived from the novel qualities of the compositions according to thisinvention are included within the ambit of the processing aspects ofthis invention.

The two-component blend upon which this invention is based results fromthe discovery of the phenomenon that certain ethoxy alkoxy-alcohol andalkylphenol sulfates improve the solubility, in electrolyte solutions,of a particular group .of phosphate esters of aliphatic 8- carbonalcohols. This group of phosphate esters ineludes the reaction productsof individual isomeric aliphatic octanols, or isomeric mixtures of theoctanols, with P 0 POCI PCL or polyphosphoric acid. The reactionproducts contain a complex mixture of phosphate esters which may or maynot contain polyphosphates and/or residual octyl alcohols.

It has been noted that when such phosphate esters, which exhibitexcellent wettability agents, are added to aqueouselectrolyte-containing solutions and more particularly to textile bathscontaining alkalies and/or other electrolytes, their solubility isreduced. The presence of the electrolytes so reduces the solubility ofthe phosphate esters that their concentrations in the solutions arebelow that at which they are effective wetting agents. Visually, in thepresence of electrolytes, the solutions of the phosphates become turbid,and upon testing, their wetting efficiencies are reduced below effectivelevels.

1 have found surprisingly that by blending at least thirty percent (30%)by weight of certain alkoxylated alcohol and alkylphenol sulfates withthe aforementioned phosphates, the solubility and wettability of thephosphate esters, in the presence of electrolytes, is reinstated andincreased and that the blend of these two components forms a compositionthat provides excellent detergency for broad spectrum use in thewetprocessing of textiles.

The aforementioned sulfate esters having these qualities arecharacterized by the formula:

where R is an alkyl radical containing 9-16 carbon atoms, or analkylphenyl group in which the alkyl substituents contain a total of6-12 carbon atoms; R is H, or a mixture of H and CH wherein thealkoxylate mixture exhibits hydrophilic properties; x is a numbercorresponding to ten to seventy percent (10% to 70%) alkoxy by weight ofthe nonionic intermediate, andM is a water-solubilizing cation.

The R substituents may be derived from commercial alkanol andalkylphenol mixtures. The alkoxylated alcohol and alkylphenol sulfatescorresponding to the above formula may be prepared as set forth in theUS. Pat. No. 2,766,212 which discloses among others, the preparation ofcompounds within the scope of these particularly effective sulfates.

M is a water solubilizing cation for the ethoxylated alkanol esters.These solubilizing cations include the ions of the alkali metals, thealkaline earth metals, Nl-l morpholine, mono-, di-, or tri-ethanolaminesor other low-molecular weight, water-solubile amines.

The octanol phosphate esters that are the other of the necessarycomponents of the blended composition of this invention are the productof the reaction of octanols with P POCl PC];; or polyphosphoric acidleading to a complex mixture of phosphate esters including varyingproportions of mono-, di-, and triphosphates. The reaction products maybe completely esterified or may include polyphosphates and/or residualoctyl alcohols. The phosphate esteriflcation reaction is carried outaccording to procedures generally practiced in the industry.

Polyphosphoric acids may be used having phosphoric acid anhydridecontents expressed as P 0 of about eighty to eighty-five percent (80% to85%) or P 0 itself may be used directly in the process as described inU.S. Pats. No. 3,004,056 and 3,004,057. The products useful as thephosphate ester components of this invention differ from those describedas resulting from the reactions set forth in the aforesaid patents inthat they are phosphate esters of aliphatic octanols and are without thealkoxylate groupings shown in the compounds of the references. Thereaction proportions and conditions are within the scope of theteachings of said patents which are herein incorporated by reference.

POCl may also be used as a phosphating agent in accordance with commonesterification procedures and the products of such a reaction withaliphatic octanols are similarly effective components of thecompositions of this invention.

The octanols for esterification by the phosphating agents describedabove include n-octanol, iso-octanol, 2-ethylhexanol and the othercommercially available octanol isomers and include the commerciallyavailable mixtures of octanols designated as C-18 alcohol blends.

When the two components of the compositions of this invention areblended, they may be utilized by solution from their dry form in themixture or the blended components may be dissolved to form stocksolutions. The stock solutions may also be prepared by the directsolution of each component in the stock solution solvent, which ispreferably water. All the blended compositions within the limits of thisinvention are soluble in solutions containing up to at least sevenpercent (7%) by weight of free sodium hydroxide and in solutionscontaining up to at least ten percent 10%) by weight of salts commonlyused in textile wet-processing. Similarly, the compositions within thescope of this invention require very low concentrations to yieldstandard wetting-times by the Draves Textile Wetting Test (ATCC) insalt-containing solutions. All the compositions according to thisinvention showed 25-second Draves Wetting Times in the presence of sevenpercent (7%) of sodium hydroxide at concentrations by weight below 0.050percent (0.050%) of the total solution of the active blend.

An additional advantage of the compositions formulated within the limitspropounded for this invention is the fact that they exhibit little ifany foaming. Any foams that form under conditions of violent agitationwere unstable and were quickly and spontaneously dissipated.

In general, it was found that the compositions of this invention wereeffective when used in textile wetprocessing solutions within the rangeof 0.01 percent (0.01%) to 1.0% by weight with the range of 0.05 percent(0.05%) to 0.15 percent (0.15%) being preferred as effective andeconomically feasible in both bleaching and scouring baths containingseven percent (7%) sodium hydroxide or its equivalent. For wool scouringbaths using sodium sulfate and sodium bisulfate, concentrations of 0.10percent (0.10%) by weight of the blend to the total bath were botheconomical and effective.

For the purpose of demonstrating the effectiveness of the compositionsof this invention, various blends ofcompositions within the scope ofthis invention were prepared and solutions thereof in electrolytes werecompared with the components of the blends alone, or blends of certaineffective components with other components bordering upon but outsidethe limits found to be effective for this invention. These solutionswere evaluated for wettability in seven percent (7%) caustic solutionsby the Draves Textile Wetting Test using 5- gram cotton skeins and3-gram hooks. The surfactant materials were added to the seven percent(7%) caustic solution and the percentage concentration of the surfactantblend required for a 25-second wetting time was determined.

In addition, the compositions that had been compared for wettabilitywere compared forsolubility at 0.05 percent (0.05%) and evaluated byvisual observation. A clear solution indicated solubility of thecomposition, whereas turbidity was an indication that the a. 30 to 90parts by weight of phosphate ester reaction products of phosphoratingagents and eightcarbon alcohols, and;

b. 70 to 10 parts by weight of a compound of the formula:

were the subject of the comparison and lie both within 10 where R is analkyl radical containing 9 to l6-carbon and without the ambit of thisinvention.

Phosphated atoms or an alkylphenyl grouping in which the alkyl ExamplePhosphate Sulfate Alkanol R X M Solub Draves** l 75 25 2-ethylhexanolAlfol 810 2.5 NH, S 0033 (C alkanol blend) 2 75 25 iso-octanol Alfol 8l02.5 NH 0.042 3 80 20 iso octanol Alfol 810 2.5 NH S 0.053 4 50 50iso-octanol Alfol 810 2.5 NH S 0052 5* 100 2-ethylhcxanol T 0.100 6* 100iso-octanol T 0.088 7 75 25 iso-octanol Neodol 25 3 K S 0.36

(C,, alkanol blend) 8* 75 25 lethylhcxanol C alkanol l.5 NH. T 0.063 9*75 25 Z-ethylhexanol 2-octanol 4 NH T 0.067 10 75 25 Z-ethylhexanolAlf0l-l0l4 5 NH S 0046 (C -C blend) H gcthylhcxanol NC,; H 0 3.3 NH, S0.042 -ethylhexanol C H 0 5.83 NH 5 0.054 13 75 25 2-ethylhexanol Calkanol blend 4 NH S 0.048 14* 75 25 2-ethylhexanol oleyl alkanol blend7 NH T 0.280 15 75 Z-cthylhcxanol N-C H 0 l0 NH S 0.047

" Comparative Example /l composition for 25-sccond wetting S Soluble TTurhid As is set forth above, the invention comprises the formulation ofa blend of the two specific classes of compounds set f6rth in theirspecified concentration ranges. This, of course, does not preclude theinclusion into commercial compositions, according to this invention, ofother ingredients useful for their specific purposes in the preparationof specific textile wetprocessing baths. These include dyestuffs,buffers, hand improvers, lusterants, and weighing agents among others.

I claim: 1

LA. textile wet-processing bath of improved detergency comprising anaqueous solution containing the functional bath agents; up to 10% ofelectrolytes; and up to 1% by weight of said bath of a detergent blendof surfactants consisting essentially of substituents contain a total of6 to 12-carbon atoms; R is H or a mixture of H and CH wherein thealkyloxylate mixture exhibits hydrophilic properties; x is a numbercorresponding to 10% to 70% alkoxylate by weight of the nonionicintermediate; and M is a watersolubilizing cation.

2. The textile bath according to claim 1 wherein the electrolyte is analkali hydroxide.

3. The textile bath according to claim 1 wherein the bath is a scouringbath.

4. The textile bath according to claim 1 wherein the bath is a bleachingbath.

5. The method of textile wet-processing which comprises immersing thetextile goods in a wetprocessing bath according to claim 1.

1. A TEXTILE WET-PROCESSING BATH OF IMPROVED DETERGENCY COMPRISING ANAQUEOUS SOLUTION CONTAINING THE FUNCTIONAL BATH AGENTS; UP TO 10% OFELECTROLYTES; AND UP TO 1% BY WEIGHT OF SAID BATH OF A DETERGENT BLENDOF SURFACTANTS CONSISTING ESSENTIALLY OF A. 30 TO 90 PARTS BY WEIGHT OFPHOSPHATE ESTER REACTION PRODUCTS OF PHOSPHORATING AGENTS ANDEIGHT-CARBON ALCOHOLS, AND; B. 70 TO 10 PARTS BY WEIGHT OF A COMPOUND OFTHE FORMULA:
 2. The textile bath according to claim 1 wherein theelectrolyte is an alkali hydroxide.
 3. The textile bath according toclaim 1 wherein the bath is a scouring bath.
 4. The textile bathaccording to claim 1 wherein the bath is a bleaching bath.
 5. The methodof textile wet-processing which comprises immersing the textile goods ina wetprocessing bath according to claim 1.